Fungicidal mixtures

ABSTRACT

Fungicidal compositions comprising an acceptable carrier and/or surface active agent and synergistically effective amounts of 
     (a) at least one azolopyrimidine of formula I                    
      in which 
     R 1 , R 2 , L 1 , L 2  and L 3  have the meaning given in claim 1; and 
     (b) at least one fungicidal active ingredient selected from benomyl, carboxin, captan, chlorothalonil, copper oxychloride, cyprodinil, dimethomorph, dithianon, dodine, famoxadone, fenhexamid, fenpiclonil, fenpropimorph, fluazinam, mancozeb, metalaxyl, pyrimethanil, quinoxifen, sulfur, triforine, vinclozolin, a fungicidal triazole derivative, and a synthetic strobilurine derivative. The invention also provides a method of controlling the growth of phytopathogenic fungi at a locus by applying synergistically effective amounts of at least one azolopyrimidine of formula I and at least one fungicidal active ingredient (b) to the locus.

This application claims the benefit of U.S. Provisional Application Ser.No. 60/101,769, filed Sep. 25, 1998.

BACKGROUND OF THE INVENTION

The present invention relates to a fungicidal composition comprising afungicidally acceptable carrier and/or surface active agent andsynergistically effective amounts of

(a) at least one azolopyrimidine of formula I

 in which

R¹ represents a C₁₋₆ alkyl, C₃₋₆ alkenyl or C₁₋₆ haloalkyl group, or

R² represents a hydrogen atom or a C₁₋₆ alkyl group, or

R¹ and R² taken together represent a C₃₋₈ alkylene group,

L¹ represents a halogen atom;

L² and L³ each independently represent a hydrogen or a halogen atom; and

and at least one fungicidal active ingredient selected from thefollowing classes (A), (B) and (C):

(A) a compound selected from the group consisting of benomyl, carboxin,captan, chlorothalonil, copper oxychloride, cyprodinil, dimethomorph,dithianon, dodine, famoxadone, fenpiclonil, fenpropimorph, fluazinam,mancozeb, metalaxyl, pyrimethanil, quinoxifen, sulfur, triforine andvinclozolin;

(B) a fungicidal triazole derivative; and

(C) a synthetic strobilurine derivative.

The fungicidal compounds of formula I to be used according to thepresent invention are known from U.S. Pat. No. 5,593,996. The compoundsof the classes (A) and (B) are known from “The Pesticide Manual”, 11thedition (1997), Editor Clive Tomlin. Fenhexamid is known from AGROW No.287, p. 21. The synthetic strobilurines are known, for example, from WO92/08703, EP 0 253 213 and EP 0 398 692.

However, none of the above mentioned prior art references teaches acombination of compounds of formula I with any of the fungicidal activeingredients selected from the classes (A), (B) and (C) as describedabove, nor that such mixtures show synergistic effects and canadvantageously be used for controlling diseases such as wheat powderymildew, barley powdery mildew, wheat leaf rust, barley net blotch andwheat Septoria leaf blotch, Botrytis diseases and others.

Surprisingly, when compounds of formula I were tank mixed with compoundsfrom classes (A), (B) and (C) and used in greenhouse and field trials, asynergistic increases in activity were observed, compared to theactivity expected based on the activities of the individual activeingredients.

A mixture of fungicides shows synergistic effect if the fungicidalactivity of the mixture is larger than the sum of activities of theseparately applied compounds. The expected fungicidal activity for agiven mixture of two fungicides can also be calculated as follows (SeeColby, S. R., “Calculating synergistic and antagonistic response ofherbicide combinations”, Weeds 15, pp 20-22 (1967):

EE=x+y−x·y/100

wherein

x is the efficacy in % compared with an untreated control upon treatmentwith a fungicidal active ingredient A at a dose rate a;

y is the efficacy in % compared with an untreated control upon treatmentwith a fungicidal active ingredient B at a dose rate b;

EE is the expected efficacy with a combination of fungicidal activeingredients A and B at a dose of a+b, respectively.

If the actual efficacy (E) exceeds the expected (calculated) one (EE),the mixture displays a synergistic effect.

SUMMARY OF THE INVENTION

The present invention includes a fungicidal composition comprising anacceptable carrier and/or surface active agent and synergisticallyeffective amounts of at least one compound of formula I, and at leastone fungicidal active ingredient selected from the following classes(A), (B) and (C):

(A) a compound selected from the group consisting of benomyl, carboxin,captan, chlorothalonil, copper oxychloride, cyprodinil, dimethomorph,dithianon, dodine, famoxadone, fenpiclonil, fenpropimorph, fluazinam,mancozeb, metalaxyl, pyrimethanil, quinoxifen, sulfur, triforine andvinclozolin;

(B) a fungicidal triazole derivative; and

(C) a synthetic strobilurine derivative.

The present invention also includes a method of controlling the growthof phytopathogenic fungi at a locus which comprises applyingsynergistically effective amounts of at least one azolopyrimidine offormula I and at least one fungicidally active ingredient selected fromclasses (A), (B) and (C) defined above to the locus.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred compounds of formula I are those wherein R¹ and R² togetherwith the interjacent nitrogen atom represent a 4-methylpiperidine ring,or wherein R¹ represents a C₁₋₆ alkyl, in particular an isopropyl group,a C₁₋₆ haloalkyl, in particular a 2,2,2-trifluoroethyl or a1,1,1-trifluoroprop-2-yl group, or a C₃₋₈ cycloalkyl group, inparticular a cyclopentyl or cyclohexyl group and R² represents ahydrogen atom, and/or wherein L¹ represents a fluorine or chlorine atomand L² and L³ each independently represent a hydrogen atom or a fluorineatom, in particular wherein L¹ represents fluorine, L² representshydrogen and L³ represents chlorine or wherein L¹ through L³ representfluorine.

Particularly preferred are the following azolopyrimidines:5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperid-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidinecoded Azoloyrimidine A,5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2,2,2-trifluoroethylamino)-[1,2,4]triazolo[1,5-a]pyrimidinecoded Azoloyrimidine B and5-chloro-6-(2,4,6-trifluorophenyl)-7-(1,1,1-trifluoroprop-2-ylamino)-[1,2,4]triazolo[1,5-a]pyrimidinecoded Azoloyrimidine C. Azolopyrimidine C due to the chirality of its1,1,1-trifluoroprop-2-yl group may be applied as a racemic mixture or inthe form of an enantiomeric enriched compound, in particular as(S)-enantiomer coded (S)-Azolopyrimidine C.

Preferred triazole derivatives in the practice of this invention are thecompounds of formula II,

 wherein

L represents a linking group selected from the groups (a), (b), (c) and(d)

 in which

X¹ represents an alkyl or an optionally substituted phenyl group;

X² and X³ each independently represent a hydrogen atom or an alkylgroup;

X⁴ represents an alkyl or cyclopropylalkyl group;

q is 1 or 2; and

n is 0 or 2.

Particularly preferred are the triazoles selected from the groupconsisting of cyproconazole, epoxiconazole, metconazole, propiconazoleand tebuconazole.

Preferred strobilurine derivatives in the practice of this invention arethe compounds of formula III,

 wherein

A represents N or CH;

B represents a —O—, —OCH₂—, a —CH₂O—, a pyrimid-4,6-dioxydiyl group or a

 group of formula

R³ represents a C₁₋₄ alkyl group;

R⁴ represents a C₁₋₆ alkoxy or a C₁₋₆ alkylamino group;

R⁵ represents a hydrogen or halogen atom or a cyano, a C₁₋₄ alkyl or aC₁₋₄ haloalkyl group; and

m is 0, 1 or 2;

in particular azoxystrobin, kresoxim methyl, CGA-279202 (AGROW 279, p.17 1998) or SSF126 (Pesticide Manual, loc. cit., page 1114)

Preferred compositions of this invention comprise the followingconstituents:

a carrier agent;

at least one azolopyrimidine of formula I,

at least one compound selected from the classes (A), (B) and (C) asdefined above;

optionally an adjuvant selected from the group consisting ofpolyalkoxylated alcohols, triglycerides and amines, in particularSynperonic 91-6, which is commercially available from ICI Surfactants;

optionally a foam breaking agent, in particular a mixture ofperfluoroalkyphosphonic acids and/or perfluoroalkylphosphinic acids, inparticular Defoamer SF or Fluowett PL, which are commercially availablefrom Clariant GmbH.

The compound of formula I and the compound selected from the classes(A), (B) and (C) as defined above are to be applied together, insynergistically effective amounts. These synergistic mixtures exhibit anextraordinary efficacy against a broad range of phytopathogenic fungi,in particular against fungi from the classes ascomycetes,basidiomycetes, oomycetes and deuteromycetes. Therefore, they can beapplied advantageously against a broad range of diseases in differentcrops. They may be applied as leaf, stem, root, into-water, seeddressing, nursery box or soil fungicides.

The composition according to the invention may be preferably applied forcontrolling phytopathogenic fungi of the genera: Achlya, Alternaria,Balansia, Bipolaris, Blumeria (Erysiphe), Cercospora, Cochliobolus,Curvularia, Cylindrocladium, Drechslera, Entyloma, Fusarium,Gaeumannomyces, Gerlachia, Gibberella, Guignardia, Leptosphaeria,Magnaporthe, Mucor, Mycosphaerella, Myrothecium, Nigrospora,Peronospora, Phoma, Pseudoperonospora, Pseudocercosporella,Phytophthora, Puccinia, Pyricularia, Pythium, Rhizoctonia, Rhizopus,Sarocladium, Sclerophthora, Sclerotium, Septoria, Tilletia, Uncinula,Ustilago, Ustilaginoidea, and Venturia, in particular the speciesBlumeria graminis f. sp. tritici, Botrytis cinerea, Septoria triticiErysiphe cichoracearum and Puccinia recondite.

The compositions according to the invention are preferably applied forcontrolling the above phytopathogenic fungi on monocotylydoneous plants,such as barley and wheat, rice and turf grases, or fruit crops such aspomefruits, stonefruits and vines, as well as all kinds of vegetables,oil and oil seed crops, and ornamentals.

The application rate of the compound of formula I according to thisinvention is suitably in the range of 1 to 2000 grams of activeingredient (g a.i.) per hectare, with rates between 20-500 g a.i./haoften achieving satisfactory control. The optimal rate for a specificapplication will depend on the crop(s) under cultivation and thepredominant species of infesting fungi, and readily may be determined byestablished biological tests known to those skilled in the art.

In general, the preferred application rate of the compounds of formula Iis in the approximate range of 10 to 500 g a.i./ha, more preferably20-300 g a.i./ha.

The optimal rate for the compounds of classes (A), (B) and (C), will,however, depend on the crop(s) under cultivation and the level ofinfestation by the fungus, and can readily be determined by establishedbiological tests.

The approximate ratio (by weight) of the compound of formula I to thefungicidal active ingredient of the classes (A), (B) and (C) is suitablyfrom 1:100 to 100:1. The preferred ratio formula I : (A), (B) or (C) mayvary, e.g., from about 1:50 to about 50:1, in particular from about 1:4to about 4:1, most preferably from 1:1.5 to 1.5:1.

The active compounds can be co-formulated together in a suitable ratioaccording to the present invention, together with carriers and/oradditives known in the art.

A method of making such a composition is also provided which comprisesbringing the compound of formula I and the fungicidal active ingredientselected from the classes (A), (B) and (C) as defined above intoassociation with at least one carrier. It is also envisaged thatdifferent isomers or mixtures of isomers of formula I and/or thefungicidal active ingredient selected from the classes (A), (B) and (C)may have different levels or spectra of activity and thus compositionsmay comprise individual isomers or mixtures of isomers.

A composition according to the invention preferably contains from 0.1%to 99.9%, preferably 0.2 to 80% by weight (w/w) of active ingredients.

A carrier in a composition according to the invention may be anymaterial with which the active ingredients may be formulated tofacilitate application to the locus to be treated (which may, forexample, be a plant, seed, foliage, soil, or into the water where theplant grow or to the roots), or to facilitate storage, transport orhandling. A carrier may be a solid or a liquid, including material whichis normally a gas but which has been compressed to form a liquid.

The compositions may be manufactured into, e.g., emulsion oremulsifiable concentrates, solutions, oil in water emulsions, wettablepowders, soluble powders, suspension concentrates, dusts, granules,aerosols, water dispersible granules, tablets, micro-capsules, gels andother formulation types by well-established procedures. These proceduresmay include intensive mixing and/or milling of the active ingredientswith other substances, such as fillers, solvents, solid carriers,surface active compounds (surfactants), and, optionally solid and/orliquid auxilaries and/or adjuvants. The form of application such asspraying, atomizing, dispersing or pouring may be chosen like thecompositions according to the desired objectives and the givencircumstances.

Solvents used in the composition of this invention may be aromatichydrocarbons, e.g. Solvesso® 200, substituted naphthalenes, phthalicacid esters, such as dibutyl or dioctyl phthalate, aliphatichydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols aswell as their ethers and esters, e.g. ethanol, ethyleneglycol mono- anddimethyl ether, ketones such as cyclohexanone, strongly polar solventssuch as N-methyl-2-pyrrolidone, or γ-butyrolactone, higher alkylpyrrolidones, e.g. n-octylpyrrolidone or cyclohexylpyrrolidone,epoxidized plant oil esters, e.g. methylated coconut or soybean oilester and water. Mixtures of different solvents may be suitable.

Solid carriers used in the composition of this invention which may beused for dusts, wettable powders, water dispersible granules, orgranules, may be mineral fillers, such as calcite, talc, kaolin,montmorillonite or attapulgite or others. The physical properties may beimproved by addition of highly dispersed silica gel or polymers.Carriers for granules may be porous material, e.g., pumice, kaolin,sepiolite, bentonite; non-sorptive carriers may be calcite or sand orothers. Additionally, a multitude of pre-granulated inorganic or organicmaterials may be used, such as dolomite or crushed plant residues.

Pesticidal compositions are often formulated and transported in aconcentrated form which is subsequently diluted by the user beforeapplication. The presence of small amounts of a carrier which is asurfactant facilitates this process of dilution. Thus, preferably atleast one carrier in a composition according to the invention is asurfactant. For example, the composition may contain two or morecarriers, at least one of which is a surfactant.

Surfactants may be nonionic, anionic, cationic or zwitterionicsubstances with good dispersing, emulsifying and wetting properties,depending on the nature of the active ingredients to be formulated.Surfactants may also include mixtures of individual surfactants.

Wettable powders in this invention suitably may contain about 5 to 90%w/w of active ingredient and, in addition to solid inert carrier, about3 to 10% w/w of dispersing and wetting agents and, where necessary, 0 to10% w/w of stabilizer(s) and/or other additives such as penetrants orstickers. Dusts may be formulated as a dust concentrate having a similarcomposition to that of a wettable powder but without a dispersant, andmay be diluted in the field with further solid carrier to give acomposition containing about 0.5 to 10% w/w of active ingredient. Waterdispersible granules and granules may have a size approximately between0.15 mm and 2.0 mm, and may be manufactured by a variety of techniquesknown in the art. These granules suitably will contain about 0.5 to 90%w/w active ingredient and 0 to 20% w/w of additives such as stabilizer,surfactants, slow release modifiers and binding agents. Emulsifiableconcentrates suitably may contain, in addition to a solvent or a mixtureof solvents, approximately 1 to 80% w/v active ingredient, 2 to 20% w/vemulsifiers and 0 to 20% w/v of other additives, such as stabilizers,penetrants and corrosion inhibitors. Suspension concentrates may bemilled so as to obtain a stable, non-sedimenting flowable product andsuitably contain about 5 to 75% w/v active ingredient, and 0.5 to 15%w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such asprotective colloids and thixotropic agents, 0 to 10% w/v of otheradditives such as defoamers, corrosion inhibitors, stabilizers,penetrants and stickers, and water or an organic liquid in which theactive ingredient is substantially insoluble; certain organic solids orinorganic salts may be present dissolved in the formulation to assist inpreventing sedimentation and crystalization or as antifreeze agents.

Aqueous dispersions and emulsions, for example compositions obtained bydiluting the formulated product according to the invention with water,also lie within the scope of the invention.

The invention also encompasses the use of a carrier which will provideslow release of the pesticidal compounds into the environment of a plantwhich is to be protected, to extend the duration of the protectiveactivity of the composition.

The biological activity of the active ingredients may be increased byincluding an adjuvant in the formulation or a spray dilution. Anadjuvant is defined here as a substance which can increase thebiological activity of an active ingredient but is not itselfsignificantly biologically active. The adjuvant can either be includedin the formulation as a coformulant or carrier, or can be added to thespray tank together with the formulation containing the activeingredient.

As a commodity, the compositions may preferably be in a concentratedform whereas the end user generally employs diluted compositions. Thecompositions may be diluted to a concentration down to about 0.001% ofactive ingredient. The doses preferably are in the approximate rangefrom 0.01 to 10 kg a.i./ha.

Examples of formulations useful in the practice of the invention are:

SC-I 1 active ingredient Azolopyrimidine C 100.0 g Dispersing agentMorwet D425 ¹⁾ 25.0 g Dispersing agent Pluronic ® PE105002 ²⁾ 5.0 gAntifoaming agent Rhodorsil ® 426R ³⁾ 1.5 g Dispersing agent Rhodopol ®23 ³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agentProxel ® GXL ⁴⁾ 1.0 g Water to 1000 ml SC-I 2 active ingredientAzolopyrimidine C 100.0 g Dispersing agent Soprophor ® FL ³⁾ 30.0 gAntifoaming agent Rhodorsil ® 426R 3) 1.5 g Dispersing agent Rhodopol ®23 ³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agentProxel ® GXL ⁴⁾ 1.0 g Water to 1000 ml SC-A/B/C active ingredientselected from classes (A), (B), (C) 200.0 g Dispersing agent Soprophor ®FL ³⁾ 25.0 g Antifoaming agent Rhodorsil ® 426R ³⁾ 1.5 g Dispersingagent Rhodopol ® 23 ³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 gBiocidal agent Proxel ® GXL ⁴⁾ 1.0 g Water to 1000 ml SC-I + A/B/Cactive ingredient Azolopyrimidine C 60.0 g active ingredient selectedfrom classes (A), (B) and (C) 120.0 g Dispersing agent Soprophor ® FL ³⁾25.0 g Antifoaming agent Rhodorsil ® 426R ³⁾ 1.5 g Dispersing agentRhodopol ® 23 ³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 gBiocidal agent Proxel ® GXL ⁴⁾ 1.0 g Water to 1000 ml DC-I 1 activeingredient Azolopyrimidine A 100.0 g Wetting agent Pluronic ® PE6400 ²⁾50.0 g Dispersing agent Lutensol ® TO 12 ²⁾ 50.0 g Solvent benzylalcohol to 1000 ml ¹⁾ Product commercially available from Witco ²⁾Product commercially available from BASF AG, Germany ³⁾ Productcommercially available from Rhône-Poulenc ⁴⁾ Product commerciallyavailable from Zeneca

The formulation SC-A/B/C, comprising a compound selected from theclasses (A), (B) and (C), may be mixed with any of the otherformulations SC-I 1, SC-I 2, SC-I 3, or DC-I which comprise theAzolopyrimidine C to produce a composition of this invention.

In a preferred embodiment of the invention, each active ingredient isadded to a tank mix in a separate formulation, to form a composition ofthis invention.

The present invention also relates to a kit for the preparation of aspray mixture consisting of two separate units:

(i) a unit which comprises at least one azolopyrimidine of formula I, inparticular one or more compounds selected from the Azolopyrimidines A, Bor C, conventional carriers and optionally adjuvants;

(ii) a unit which comprises at least one active ingredient selected fromthe classes (A), (B) and (C), preferably one or more compounds selectedfrom the group consisting of carboxin, fluazinam, quinoxifen, metalaxyl,famoxadone, metconazole, epoxiconazole, propiconazole, azoxystrobin orkresoxim methyl conventional carriers and optionally adjuvants.

In a preferred embodiment, the kit includes two bottles with dispensingmeans which allow the easy and correct addition of the activeingredients to the tank mix.

A composition according to the invention preferably contains from about0.5% to 95% by weight of active ingredients.

The compositions of this invention may be diluted down to aconcentration of about 0.0001% of active ingredients.

The compositions of this invention can be applied to the plants or theirenvironment simultaneously with or in succession with other activesubstances. These other active substances can be either fertilizers,agents which donate trace elements, or other preparations whichinfluence plant growth. However, they can also be other fungicides,selective herbicides, insecticides, bactericides, nematicides,algicides, molluscidides, rodenticides, virucides, compounds inducingresistance into plants, biological control agents such as viruses,bacteria, nematodes, fungi and other microorganisms, repellents of birdsand animals, and plant growth regulators, or mixtures of several ofthese preparations, if appropriate together with other carriersubstances conventionally used in the art of formulation, surfactants orother additives which promote application.

Examples of insecticidal compounds useful in this invention arealpha-cypermethrin, benfuracarb, BPMC, buprofezine, carbosulfan, cartap,chlorfenvinphos, chlorpyrifos-methyl, cycloprothrin, cypermethrin,esfenvalerate, ethofenprox, fenpropathrin, flucythrinate, flufenoxuron,hydramethylnon, imidacloprid, isoxathion, MEP, MPP, nitenpyram, PAP,permethrin, propaphos, pymetrozine, silafluofen, tebufenozide,teflubenzuron, temephos, terbufos, tetrachlorvinphos and triazamate.

Examples of biological control agents useful in this invention are:Bacillus thuringiensis, Verticillium lecanii, Autographica californicaNPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtilis,Pseudomonas fluorescens, Steptomyces griseoviridis and Trichodermaharzianum.

Examples of chemical agents that induce systemic acquired resistance inplants are: isonicotinic acid or derivatives thereof,2,2-dichloro-3,3-dimethylcyclopropylcarboxylic acid and BION.

The present invention is of wide applicability in the protection ofcrops, trees, residential and ornamental plants against fungal attack.Preferred crops are cereals, such as wheat and barley, rice, vines, andapples. The duration of the protection is normally dependent on theindividual compound selected, and also a variety of external factors,such as climate, the impact of which may be mitigated by the use of asuitable formulation.

The following examples further illustrate the present invention. Itshould be understood, however, that the invention is not limited solelyto the particular examples given below.

EXAMPLES

General Methods

The trials are carried out under greenhouse (Examples 1 to 32) or fieldconditions (Examples 33 to 40) in residual or curative applications. Thefungicides are applied in single treatments, or in a combinationcomprising an azolopyrimidine of formula I and a compound selected fromthe classes (A), (B) and (C) as defined above. The compounds are appliedin form of an aqueous spray mix obtained from a concentrated formulationor the technical material.

1. Cereals and Dicots—Greenhouse

1. Seed is planted in 6 cm diameter plastic pots and maintained in thegreenhouse.

2. When the primary leaf is fully expanded in the case of cereals orseveral leaves are present in the case of dicots, formulated testcompounds are sprayed with a three nozzle overhead fungicide sprayer tonear run-off. Alternatively, a single nozzle overhead track sprayer isused for application of the compounds to cereals at a rate of 200 I/ha.Plants are then allowed to air-dry.

3. Inoculation precedes treatment in the case of curative evaluationsand follows treatment in case of residual evaluations. For inoculationof powdery mildew disease, plants are set up on greenhouse benches withbottom watering mats and inoculated by dusting them with conidia frominfected plants. Between inoculation and treatment for curativeevaluations and between treatment and inoculation for residualevaluations, plants are maintained in the greenhouse with bottomwatering. For inoculation of non-powdery mildew diseases, an aqueousspore suspension of the pathogen is applied to the plant and the plantsare kept 1-2 days in a moist infection chamber before being returned tothe greenhouse where they are maintained by bottom watering.

4. Disease on the foliage as percent leaf area with diseasesymptoms/signs is evaluated about 7 days after inoculation. In the caseof wheat, the tips and bases of the leaves are excluded from theevaluation.${\% \quad {disease}\quad {control}} = {100 - {\frac{\% \quad {disease}\quad {in}\quad {treated}\quad {plants}}{\% \quad {disease}\quad {in}\quad {untreated}\quad {plants}} \times 100\%}}$

Formulation, Reference Compounds and Controls

1. Technical compounds are formulated in a solvent/surfactant systemconsisting of 5% acetone and 0.05% Tween 20 in deionized water.Compounds are dissolved in acetone prior to addition of the water; theTween 20 can be added through either the acetone or the water. Dilutionsare made using the solvent/surfactant system Formulated compounds areprepared using deionized water.

2. Two kinds of controls are included: Plants treated with thesolvent/surfactant solution and inoculated (Solvent Blank). Untreatedplants which are inoculated (Inoculated Control).

For the field study formulated Azolopyrimidine A, B or C and formulatedcompounds from the classes (A), (B) and (C) were used.

Evaluation of the Disease

Assessments of the diseases took place at the indicated day after theapplication of the compounds. Per cent infected leaf area infected wasevaluated. The efficacy of the compounds/compounds mixtures to controlthe diseases was calculated by using the formula given above under item4:

II. Apple Fruit Botrytis

1. Apples (Malus X domestics Borkh.) variety Golden Delicious aredisinfected by washing them briefly in 70% ethanol. After drying theapples are marked with four short equal-distant lines indicating thepositions to be wounded.

2. Corresponding with the marks, four holes are poked around the appleequator with a pipette tip. 10 μl of the treatment solution are pipettedinto each hole.

3. Three hours after application, 10 μl of a conidial suspension ofBotrytis cinerea are pipetted into each. For incubation, thetreated/inoculated apples are set up for five days.

4. Disease occurs as rotten apple tissue surrounding the inoculatedwounds. The diameter of the rotten zone around each wound is measured.

Formulation, Reference Compounds and Controls

1. Technical compounds are formulated in a solvent system consisting of5% acetone and 0.05% Tween 20 in deionized water. Compounds aredissolved in acetone prior to dilution with water. Formulated compoundsare prepared using deionized water.

2. Three kinds of controls are included: Apples treated with the solventsolution and inoculated (Solvent Blank). Untreated apples which areinoculated (Inoculated Control). Untreated apples which are notinoculated (Uninoculated Control).

Evaluation of the Disease

Assessments of the diseases took place at the indicated day after theapplication of the compounds. Per cent infected leaf area infected wasevaluated. The efficacy of the compounds/compounds mixtures to controlthe diseases was calculated by using the formula:${\% \quad {disease}\quad {control}} = {100 - {\frac{{mean}\quad {of}\quad {diameters}\quad {on}\quad {treated}\quad {apples}}{{mean}\quad {of}\quad {diameters}\quad {on}\quad {untreated}\quad {apples}} \times 100\%}}$

Determination of Synergy

calculated using the % disease control values of specific for the twoCOLBY formula given hereinabove

III. Field Tests

The compounds are applied according to good agricultural practice in theform of an aqueous spray mix obtained from a concentrated formulation orthe technical material at a rate of 400 I/ha. The disease control isevaluated according to the formula given for the greenhouse tests.

Greenhouse Tests

Example 1

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Fenpropimorph (3Day Residual) Against Leptosphaeria nodorum on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Aand an EC formulation containing 750 g fenpropimorph per liter. Theobserved and expected efficacies with different rates are given in TableI:

TABLE I dose rate (ppm) Observed Azolopyrimidine A fenpropimorphEfficacy Expected Efficacy 100 0 40 — 10 0 35 — 0 5 15 — 0 0.5 19 — 1005 71 49 100 0.5 80 51 10 5 55 45 10 0.5 50 47

Example 2

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Tebuconazole (3Day Residual) Against Leptosphaeria nodorum on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Aand an EC formulation containing 250 g tebuconazole per liter. Theobserved and expected efficacies with different rates are given in TableII:

TABLE II dose rate (ppm) Observed Azolopyrimidine A tebuconazoleEfficacy Expected Efficacy 100 0 40 — 0 0.2 19 — 0 0.02 25 — 100 0.2 8851 100 0.02 87 55

Example 3

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Tebuconazole (2Day Residual) Against Blumeria graminis on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Aand an EC formulation containing 250 g tebuconazole per liter. Theobserved and expected efficacies with different rates are given in TableIII:

TABLE III dose rate (ppm) Observed Azolopyrimidine A tebuconazoleEfficacy Expected Efficacy 10 0 14 — 0 0.2 9 — 0 0.02 2 — 10 0.2 52 2210 0.02 33 16

Example 4

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Vinclozolin (3Day Residual) Against Botrytis cinerea on Apple Fruits

The tank mix was obtained from technical material of Azolopyrimidine Aand a WG formulation containing 500 g vinclozolin per kg. The observedand expected efficacies with different rates are given in Table IV:

TABLE IV dose rate (ppm) Observed Azolopyrimidine A vinclozolin EfficacyExpected Efficacy 10 0 33 — 1 0 0 — 0 10 8 — 10 10 54 38 1 10 31  8

Example 5

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Cyprodinil (3Day Residual) Against Botrytis cinerea on Apple Fruits

The tank mix was obtained from technical material of Azolopyrimidine Aand a WG formulation containing 750 g cyprodinil per kg. The observedand expected efficacies with different rates are given in Table V:

TABLE V dose rate (ppm) Azolopyrimidine A cyprodinil Observed EfficacyExpected Efficacy 10 0 33 — 1 0 0 — 0 1 46 — 0 0.1 2 — 10 1 66 64 10 0.161 34 1 0.1 3  2

Example 6

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Benomyl (3 DayResidual) Against Botrytis cinerea on Apple Fruits The tank mix wasobtained from technical material of Azolopyrimidine A and a WPformulation containing 500 g benomyl per kg. The observed and expectedefficacies with different rates are given in Table VI:

TABLE VI dose rate (ppm) Azolopyrimidine A benomyl Observed EfficacyExpected Efficacy 10 0 25 — 1 0 0 — 0 10 13 — 0 1 0 — 10 10 87 35 10 138 25 1 10 35 13 1 1 15  0

Example 7

Fungicidal Efficacy of the Mixture of Azolopyrimidine A+Vinclozolin (3Day Residual) Against Botrytis cinerea on Apple Fruits

The tank mix was obtained from technical material of Azolopyrimidine Aand a WG formulation containing 500 g vinclozolin per kg. The observedand expected efficacies with different rates are given in Table VII:

TABLE VII dose rate (ppm) Observed Azolopyrimidine A VinclozolinEfficacy Expected Efficacy 10 0 25 — 1 0 0 — 0 10 17 — 0 1 0 — 10 10 5738 1 1 4  0

Example 8

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Metconazole (1Day Residual) Against Rhynchosporium secalis on Barley

The tank mix was obtained from technical materials of Azolopyrimidine Cand metconazole. The observed and expected efficacies are given in TableVIII:

TABLE VIII dose rate (ppm) Observed Azolopyrimidine C metconazoleEfficacy Expected Efficacy 100 0 15 — 0 100 87 — 100 100 100 89

Example 9

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Metconazole (1Day Residual) Against Septoria tritici on Wheat

The tank mix was obtained from a SC formulation containing 100 gAzolopyrimidine C per liter and an EC containing 100 g metconazole perliter. The observed and expected efficacies with different rates aregiven in Table IX:

TABLE IX dose rate (ppm) Observed Azolopyrimidine C metconazole EfficacyExpected Efficacy 40 0 91 — 25 0 68 — 8 0 0 — 5 0 0 — 2 0 0 — 0 25 0 — 010 0 — 0 8 0 — 0 5 0 — 0 2 0 — 40 10 92 91 25 25 89 68 8 2 11 0 5 5 16 02 8 28 0

Example 10

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Metconazole (1Day Residual) Against Pyrenophora teres on Barley

The tank mix was obtained from a SC formulation containing 100 gAzolopyrimidine C per liter and an EC containing 100 g metconazole perliter. The observed and expected efficacies with different rates aregiven in Table X:

TABLE X dose rate (ppm) Observed Azolopyrimidine C Metconazole EfficacyExpected Efficacy 125 0 0 — 50 0 0 — 40 0 0 — 25 0 0 — 10 0 0 — 0 200 73— 0 125 68 — 0 40 34 — 0 25 9 — 0 10 4 — 125 125 69 68 50 200 82 73 2525 46 9 40 10 9 4 10 40 51 34

Example 11

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Metconazole (1Day Residual) Against Puccinia recondita on Wheat

The tank mix was obtained from from a SC formulation containing 100 gAzolopyrimidine C per liter and an EC containing 100 g metconazole perliter. The observed and expected efficacies with different rates aregiven in Table XI:

TABLE XI dose rate (ppm) Observed Azolopyrimidine C metconazole EfficacyExpected Efficacy 200 0 35 — 125 0 20 — 40 0 10 — 25 0 5 — 10 0 3 — 8 01 — 2 0 2 — 0 125 97 — 0 50 72 — 0 40 31 — 0 25 14 — 0 10 8 — 0 8 0 — 02 0 — 200 50 86 82 125 125 99 98 40 10 25 17 25 25 22 18 10 40 70 33 8 21 1 2 8 8 2

Example 12

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Kresoxim Methyl(1 Day Curative) Against Puccinia recondita on Wheat

Plants sprayed twice, once with each compound. The tank mixes wereobtained from a SC formulation containing 100 g Azolopyrimidine C perliter and a WG containing 500 g kresoxim methyl per kg. The observed andexpected efficacies with different rates are given in Table XII:

TABLE XII dose rate (ppm) Observed Azolopyrimidine C kresoxim methylEfficacy Expected Efficacy 400 0 99 — 200 0 97 — 100 0 79 — 50 0 66 — 250 25 — 0 400 5 — 0 200 1 — 0 100 0 — 0 50 1 — 0 25 0 — 400 400 99 99 200200 94 97 100 100 86 79 50 50 84 66 25 25 29 25

Example 13

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Carboxin (1 DayResidual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand a WP formulation containing 750 g carboxin per kg. The observed andexpected efficacies with different rates are given in Table XIII:

TABLE XIII dose rate (ppm) Azolopyrimidine A carboxin Observed EfficacyExpected Efficacy 4 0 100 — 1 0 71 — 0.25 0 41 — 0.06 0 8 — 0 4 4 — 0 10 — 0 0.25 0 — 0 0.06 0 — 4 4 100 100 1 1 89 71 0.25 0.25 66 49 0.060.06 59 8

Example 14

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Fluazinam (1 dayResidual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand a SC formulation containing 500 g fluazinam per liter. The observedand expected efficacies with different rates are given in Table XIV:

TABLE XIV dose rate (ppm) Azolopyrimidine A fluazinam Observed EfficacyExpected Efficacy 4 0 100 — 1 0 71 — 0.06 0 8 — 0 4 17 — 0 1 4 — 0 0.060 — 4 4 100 100 1 1 92 72 0.06 0.06 24 8

Example 15

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+quinoxyfen (1Day Residual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand quinoxyfen. The observed and expected efficacies with differentrates are given in Table XV:

TABLE XV dose rate (ppm) Observed Azolopyrimidine A quinoxyfen EfficacyExpected Efficacy 4 0 100 — 1 0 71 — 0.25 0 49 — 0.06 0 8 — 0 4 0 — 0 10 — 0 0.25 0 — 0 0.06 0 — 4 4 100 100 1 1 95 71 0.25 0.25 54 49 0.060.06 23 8

Example 16

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Quinoxyfen (1Day Residual) Against Blumeria graminis on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand quinoxyfen. The observed and expected efficacies with differentrates are given in Table XVI:

TABLE XVI dose rate (ppm) Observed Azolopyrimidine A quinoxyfen EfficacyExpected Efficacy 4 0 96 — 1 0 42 — 0.25 0 19 — 0.06 0 0 — 0 4 99 — 0 173 — 0 0.25 18 — 0 0.06 8 — 4 4 100 100 1 1 87 85 0.25 0.25 53 33 0.060.06 24 8

Example 17

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Metalaxyl (1 DayResidual) Against Blumeria graminis on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand metalaxyl. The observed and expected efficacies with different ratesare given Table XVII:

TABLE XVII dose rate (ppm) Azolopyrimidine C metalaxyl Observed EfficacyExpected Efficacy 4 0 96 — 1 0 42 — 0.25 0 19 — 0.06 0 0 — 0 4 0 — 0 1 0— 0 0.25 0 — 0 0.06 0 — 4 4 92 96 1 1 45 42 0.25 0.25 34 19 0.06 0.06 210

Example 18

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Famoxadone (1Day Residual) Against Blumeria graminis on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand famoxadone. The observed and expected efficacies with differentrates are given in Table XVIII:

TABLE XVIII dose rate (ppm) Azolopyrimidine C Famoxadone ObservedEfficacy Expected Efficacy 4 0 96 — 1 0 42 — 0.25 0 19 — 0.06 0 0 — 0 40 — 0 1 0 — 0 0.25 0 — 0 0.06 0 — 4 4 96 96 1 1 53 42 0.25 0.25 34 190.06 0.06 9 0

Example 19

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Famoxadone (1Day Residual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand famoxadone. The observed and expected efficacies with differentrates are given in Table XIX:

TABLE XIX dose rate (ppm) Azolopyrimidine C famoxadone Observed EfficacyExpected Efficacy 4 0 100 — 1 0 71 — 0.25 0 49 — 0.06 0 8 — 0 4 61 — 0 131 — 0 0.25 0 — 0 0.06 0 — 4 4 100 100 1 1 87 80 0.25 0.25 52 49 0.060.06 29 8

Example 20

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Dodine (1 DayResidual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand a WP containing 650 g dodine per kg. The observed and expectedefficacies with different rates are given in Table XX:

TABLE XX dose rate (ppm) Azolopyrimidine C dodine Observed EfficacyExpected Efficacy 0.06 0 8 — 0 0.06 0 — 0.06 0.06 28 8

Example 21

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+CopperOxychloride (1 Day Residual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand a WP containing 450 g copper oxychloride per kg. The observed andexpected efficacies with different rates are given in Table XXI:

TABLE XXI dose rate (ppm) Azolopyrimidine copper C oxychloride ObservedEfficacy Expected Efficacy 0.06 0 8 — 0 0.06 0 — 0.06 0.06 18 8

Example 22

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Sulfur (1 DayResidual) Against Puccinia recondita on Wheat

The tank mix was obtained from technical material of Azolopyrimidine Cand sulfur. The observed and expected efficacies with different ratesare given in Table XXII:

TABLE XXII dose rate (ppm) Azolopyrimidine C sulfur Observed EfficacyExpected Efficacy 1 0 71 — 0 1 0 — 1 1 86 71

Example 23

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Triforine (1 DayResidual) Against Erysiphe cichoracearum on Cucumbers

The tank mix was obtained from a SC formulation containing 100 g ofAzolopyrimidine C per liter and an DC formulation containing and 190 gof triforine liter. The observed and expected efficacies with differentrates are given in Table XXIII:

TABLE XXIII dose rate (ppm) Azolopyrimidine C triforine ObservedEfficacy Expected Efficacy 4 0 7 — 1 0 0 — 0 16 15 — 0 4 0 — 4 16 47 341 4 12 0

Example 24

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Cyprodinil (1Day Residual) Against Erysiphe cichoracearum on Cucumbers

The tank mix was obtained from a SC formulation containing 100 g ofAzolopyrimidine C per liter and a WG formulation containing and 750 g ofcyprodinil per kg. The observed and expected efficacies with differentrates are given in Table XXIV:

TABLE XXIV dose rate (ppm) Azolopyrimidine C cyprodinil ObservedEfficacy Expected Efficacy 4 0 7 — 1 0 0 — 0 16 29 — 0 4 0 — 4 16 41 341 4 10 0

Example 25

Fungicidal Efficacy of the Mixture of Azolopyrimidine C and DifferentFungicides (1 Day Residual) Against Alternaria solani on Tomatoes

The tank mix was obtained from an SC formulation containing 100 gAzolopyrimidine A per liter and WP formulations of dithianon (750 g/kg),captan (500 g/kg), cyprodinil (750 g/kg), mancozeb (800 g/kg), or a SCformulation of chlorothalonil (500 g/l), or a FS formulation offenpiclonil (400 g/l), repectively. The observed and expected efficacieswith different rates are given in Table XXV:

TABLE XXV Azolopyrimidine C Cereal rate Observed Expected (g/ha)Fungicide (g/ha) Efficacy Efficacy 4 — 0 25 — 0 dithianon 16 50 — 0captan 16 18 — 0 cyprodinil 16 13 — 0 mancozeb 16 27 — 0 chlorothalonil16 13 — 0 fenpiclonil 16 76 — 4 dithianon 16 76 63 4 captan 16 60 38 4cyprodinil 16 50 35 4 mancozeb 16 62 45 4 chlorothalonil 16 57 35 4fenpiclonil 16 91 82

Example 26

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Fenhexamid (2 Days Curative) Against Blumeria graminis on Barley

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Fenhexamid. The active ingredients, theobserved and expected efficacies with different rates are given in TableXXVI:

TABLE XXVI dose rate Observed Expected Compound (ppm) Efficacy Efficacy(S)-Azolopyrimidine C 180 86 60 60 20 37 6.7 29 2.2 8 0.74 0 Fenhexamid180 39 60 7 20 1 6.7 0 2.2 0 0.74 0 (S)-Azolopyrimidine C + 180 + 180 9591 Fenhexamid 60 + 60 70 63 20 + 20 42 38 6.7 + 6.7 36 29 2.2 + 2.2 18 80.74 + 0.74 8 0

Example 27

Fungicidal efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Azoxystrobin or Trifloxystrobin (2 Days Curative) Against Blumeriagraminis on Wheat

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin. The activeingredients, the observed and expected efficacies with different ratesare given in Table XXVII:

TABLE XXVII dose rate Observed Expected Compound (ppm) Efficacy Efficacy(S)-Azolopyrimidine C 50 81 25 61 12.5 40 6.3 10 3.1 0 1.6 0Azoxystrobin 50 61 25 48 12.5 28 6.3 21 3.1 2 1.6 0 Trifloxystrobin 5099 25 98 12.5 89 6.3 78 3.1 55 1.6 34 (S)-Azoiopyrimidine C + 50 + 50 9593 Azoxystrobin 25 + 25 79 80 12.5 + 12.5 62 57 6.3 + 6.3 30 29 3.1 +3.1 20 2 1.6 + 1.6 14 0 (S)-Azolopyrimidine C + 50 + 50 100 100Trifloxystrobin 25 + 25 100 99 12.5 + 12.5 93 93 6.3 + 6.3 75 80 3.1 +3.1 67 55 1.6 + 1.6 45 34

Example 28

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Azoxystrobin or Trifloxystrobin (2 Days Curative) Against Pucciniarecondita on Wheat

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin. The activeingredients, the observed and expected efficacies with different ratesare given in Table XXVIII:

TABLE XXVIII dose rate Observed Expected Compound (ppm) EfficacyEfficacy S)-Azolopyrimidine C 25 54 12.5 23 6.3 8 3.1 0 1.6 0Azoxystrobin 25 95 12.5 85 6.3 48 3.1 25 1.6 0 Trifloxystrobin 25 0 12.50 6.3 0 3.1 0 1.6 0 (S)-Azolopyrimidine C + 25 + 25 99 98 Azoxystrobin12.5 + 12.5 87 88 6.3 + 6.3 81 52 3.1 + 3.1 45 25 1.6 + 1.6 18 0(S)-Azolopyrimidine C + 25 + 25 53 54 Trifloxystrobin 12.5 + 12.5 36 236.3 + 6.3 15 8 3.1 + 3.1 5 0 1.6 + 1.6 0 0

Example 29

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Azoxystrobin or Trifloxystrobin (2 Days Curative) Against Blumeriagraminis on Barley

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin. The activeingredients, the observed and expected efficacies with different ratesare given in Table XXIX:

TABLE XXIX dose rate Observed Expected Compound (ppm) Efficacy Efficacy(S)-Azolopyrimidine C 50 73 25 54 12.5 31 6.3 15 3.1 1 1.6 0Azoxystrobin 50 87 25 73 12.5 49 6.3 21 3.1 10 1.6 0 Trifloxystrobin 5096 25 89 12.5 74 6.3 59 3.1 36 1.6 22 (S)-Azolopyrimidine C + 50 + 50 9896 Azoxystrobin 25 + 25 90 88 12.5 + 12.5 75 65 6.3 + 6.3 51 33 3.1 +3.1 18 11 1.6 + 1.6 1 1 (S)-Azolopyrimidine C + 50 + 50 100 99Trifloxystrobin 25 + 25 98 95 12.5 + 12.5 87 82 6.3 + 6.3 61 65 3.1 +3.1 46 37 1.6 + 1.6 28 22

Example 30

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Azoxystrobin or Trifloxystrobin (4 Days Residual) Against Blumeriagraminis on Wheat

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin. The activeingredients, the observed and expected efficacies with different ratesare given in Table XXX:

TABLE XXX dose rate Observed Expected Compound (ppm) Efficacy Efficacy(S)-Azolopyrimidine C 50 34 25 11 12.5 3 6.3 0 3.1 0 Azoxystrobin 50 925 9 12.5 7 6.3 0 3.1 0 Trifloxystrobin 50 14 25 0 12.5 0 6.3 0 3.1 0(S)-Azolopyrimidine C + 50 + 50 49 40 Azoxystrobin 25 + 25 25 19 12.5 +12.5 18 10 6.3 + 6.3 1 0 3.1 + 3.1 0 0 (S)-Azolopyrimidine C + 50 + 5051 43 Trifloxystrobin 25 + 25 27 11 12.5 + 12.5 29 3 6.3 + 6.3 7 0 3.1 +3.1 9 0

Example 31

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Azoxystrobin or Trifloxystrobin (4 Days Residual) Against Pucciniarecondita on Wheat

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin. The activeingredients, the observed and expected efficacies with different ratesare given in Table XXXI:

TABLE XXXI dose rate Observed Expected Compound (ppm) Efficacy Efficacy(S)-Azolopyrimidine C 50 50 25 27 12.5 16 6.3 9 3.1 0 Azoxystrobin 50 825 0 12.5 0 6.3 0 3.1 0 Trifloxystrobin 50 0 25 0 12.5 0 6.3 0 3.1 0(S)-Azolopyrimidine C + 50 + 50 63 54 Azoxystrobin 25 + 25 28 27 12.5 +12.5 21 16 6.3 + 6.3 10 9 3.1 + 3.1 6 0 (S)-Azolopyrimidine C + 50 + 5059 50 Trifloxystrobin 25 + 25 35 27 12.5 + 12.5 15 16 6.3 + 6.3 10 93.1 + 3.1 1 0

Example 32

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C in Admixturewith Azoxystrobin (4 Days Residual) Against Blumeria graminis on Barley

The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin. The active ingredients, theobserved and expected efficacies with different rates are given in TableXXXII:

TABLE XXXII dose rate Observed Expected Compound (ppm) Efficacy Efficacy(S)-Azolopyrimidine C 50 28 25 22 12.5 17 6.3 8 3.1 3 1.6 0 Azoxystrobin50 9 25 2 12.5 3 6.3 3 3.1 3 1.6 0 (S)-Azolopyrimidine C + 50 + 50 39 34Azoxystrobin 25 + 25 34 24 12.5 + 12.5 27 19 6.3 + 6.3 20 11 3.1 + 3.120 6 1.6 + 1.6 14 0

B Field Tests

Example 33

Fungicidal Efficacy of the Mixture of Azolopyrimidine B+Pyrimethanil inthe Field Against Botrytis cinerea in Vines

The tank mix was obtained from a SC formulation containing 100 g ofAzolopyrimidine B per liter and a SC formulation containing 400 g ofpyrimethanil per liter. The observed and expected efficacies are givenin Table XXXIII:

TABLE XXXIII dose rate g/ha Observed Azolopyrimidine B pyrimethanilEfficacy Expected Efficacy 250 0 58 — 0 500 66 — 250 500 92 86

Example 34

Fungicidal Efficacy of the Mixture of Azolopyrimidine C+Metconazole inthe Field Against Septoria tritici on Wheat

The tank mix was obtained from an EC formulation containing 150 gAzolopyrimidine C per liter and a SL formulation containing 60 gmetconazole per liter. The observed and expected efficacies withdifferent rates are given in Table XXXIVa (19 days after application)and Table XXXIVb (25 days after application):

TABLE XXXIVa dose rate (g/ha) Observed Azolopyrimidine C MetconazoleEfficacy Expected Efficacy 25 0 48 — 0 15 9 — 0 30 36 — 0 45 24 — 25 1573 53 25 30 74 67 25 45 76 60

TABLE XXXIVa dose rate (g/ha) Observed Azolopyrimidine C MetconazoleEfficacy Expected Efficacy 25 0 48 — 0 15 9 — 0 30 36 — 0 45 24 — 25 1573 53 25 30 74 67 25 45 76 60

Example 35

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C+KresoximMethyl in the Field Against Septoria tritici on Wheat

The tank mix was obtained from a SC formulation containing 100 g(S)-Azolopyrimidine C per liter and a WG formulation containing 500 gkresoxim methyl per kg. The observed and expected efficacies withdifferent rates are given in Tables XXXVa (7 days after application),XXXVb (22 days after application), XXXVc (34 days after application),and XXXVd (41 days after application):

TABLE XXXVa dose rate (g/ha) Observed (S)-Azolopyrimidine C kresoximmethyl Efficacy Expected Efficacy 25 0 34 — 0 100 40 — 25 100 70 60

TABLE XXXVa dose rate (g/ha) Observed (S)-Azolopyrimidine C kresoximmethyl Efficacy Expected Efficacy 25 0 34 — 0 100 40 — 25 100 70 60

TABLE XXXVa dose rate (g/ha) Observed (S)-Azolopyrimidine C kresoximmethyl Efficacy Expected Efficacy 25 0 34 — 0 100 40 — 25 100 70 60

TABLE XXXVd dose rate (g/ha) Observed (S)-Azolopyrimidine C kresoximmethyl Efficacy Expected Efficacy 75 0 92 — 0 100 92 — 75 100 100 98

Example 36

Fungicidal Efficacy of the Mixture of (S)-AzolopyrimidineC+Cyproconazole in the Field Against Blumeria graminis on Wheat 17 DaysAfter Application

The tank mix was obtained from a SC formulation containing 100 g(S)-Azolopyrimidine C per liter and an EC formulation containing 60 gcyproconazole per liter. The observed and expected efficacies withdifferent rates are given in Table XXXVI:

TABLE XXXVI dose rate (g/ha) Observed (S)-Azolopyrimidine Ccyproconazole Efficacy Expected Efficacy 25 0 63 — 50 0 78 — 75 0 74 — 015 86 — 0 30 82 — 25 15 96 95 25 30 98 93 50 30 100 96 75 30 98 95

Example 37

Fungicidal Efficacy of the Mixture of (S)-Azolopyrimidine C+Azoxystrobinin the Field Against Blumeria graminis on Wheat 17 Days AfterApplication

The tank mix was obtained from a SC formulation containing 100 g(S)-Azolopyrimidine C per liter and a SC formulation containing 250 gazoxystrobin per kg. The observed and expected efficacies with differentrates are given in Table XXXVII:

TABLE XXXVII dose rate (g/ha) Observed (S)-Azolopyrimidine CAzoxystrobin Efficacy Expected Efficacy 25 0 63 — 50 0 78 — 75 0 74 —100 0 96 — 0 75 49 — 25 75 92 81 50 75 94 89 75 75 92 86 100 75 100 98

Example 38

Fungicidal Efficacy of the Mixture of Azolopyrimidine A and DifferentCereal Fungicides in the Field Against Blumeria graminis on Wheat 15Days After Application

The tank mix was obtained from an SC formulation containing 100 gAzolopyrimidine A per liter and commercially available formulations ofmetconazole, epoxiconazole or kresoxim methyl, respectively. Theobserved and expected efficacies with different rates are given in TableXXXVIII:

TABLE XXXVIII Azolopyrimidine Cereal Observed Expected A Fungicide rate(g/ha) Efficacy Efficacy 125 — 0 22 — 0 metconazole 45 54 — 0epoxiconazole 63 40 — 0 kresoxim methyl 100 85 — 125 metconazole 45 7964 125 epoxiconazole 63 74 53 125 kresoxim methyl 100 92 88

Example 39

Fungicidal Efficacy of the Mixture of Azolopyrimidine A and DifferentCereal Fungicides in the Field Against Septoria tritici on Wheat 15 DaysAfter Application

The tank was obtained from an SC formulation containing 100 gAzolopyrimidine A per liter and commercially available formulations ofmetconazole, epoxiconazole or propiconazole, respectively. The observedand expected efficacies with different rates are given in Table XXXIX:

TABLE XXXIX Azolopyrimidine Cereal Observed Expected A Fungicide rate(g/ha) Efficacy Efficacy 125 — 0 63 — 0 metconazole 45 77 — 0epoxiconazole 63 93 — 0 propiconazole 63 72 — 125 metconazole 45 99 91125 epoxiconazole 63 97 97 125 propiconazole 63 93 90

Example 40

Fungicidal Efficacy of the Mixture of Azolopyrimidine A and DifferentCereal Fungicides in the Field Against Puccinia recondita on Wheat 50Days After Application

The tank mix was obtained from an SC formulation containing 100 gAzolopyrimidine A per liter and commercially available formulations ofmetconazole, epoxiconazole, propiconazole or kresoxim methyl,respectively. The observed and expected efficacies with different ratesare given in Table XXXX:

TABLE XXXX Azolopyrimidine Cereal Observed Expected A Fungicide rate(g/ha) Efficacy Efficacy 125 — 0 0 — 0 metconazole 45 75 — 0epoxiconazole 63 95 — 0 propiconazole 63 49 — 0 kresoxim methyl 100 0 —125 metconazole 45 85 75 125 epoxiconazole 63 97 95 125 propiconazole 6367 49 125 kresoxim methyl 100 64 0

What is claimed is:
 1. A fungicidal composition comprising afungicidally acceptable carrier and/or surface active agent andsynergistically effective amounts of (a) at least one azolopyrimidine offormula I

 in which R¹ represents a C₁₋₆ alkyl, C₃₋₆ alkenyl or C₁₋₆ haloalkylgroup, or R² represents a hydrogen atom or a C₁₋₆ alkyl group, or R¹ andR² taken together represent a C₃₋₈ alkylene group, L¹ represents ahalogen atom; L² and L³ each independently represent a hydrogen or ahalogen atom; and (b) a synthetic strobilurine derivative.
 2. Acomposition as claimed in claim 1, wherein the synthetic strobilurinederivative is a compound of formula III,

wherein A represents N or CH; B represents a —O—, —OCH₂—, a —CH₂O—, apyrimid-4,6-dioxydiyl group or a group of formula

R³ represents a C₁₋₄ alkyl group; R⁴ represents a C₁₋₆ alkoxy or a C₁₋₆alkylamino group; R⁵ represents a hydrogen or halogen atom or a cyano, aC₁₋₄ alkyl or a C₁₋₄ haloalkyl group; and m 0, 1 or
 2. 3. A compositionas claimed in claim 1 containing a compound of formula I, wherein


4. A composition as claimed in claim 3, wherein the azolopyrimidine isselected from the group consisting of:5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperid-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine,5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2,2,2-trifluoroethylamino)-[1,2,4]triazolo[1,5-a]pyrimidine,and5-chloro-6-(2,4,6-trifluorophenyl)-7-(1,1,1-trifluoroprop-2-ylamino)-[1,2,4]triazolo[1,5-a]pyrimidine.5. A composition as claimed in claim 2, wherein the strobilurinederivative is selected from azoxystrobin and kresoxim methyl.
 6. Acomposition as claimed in claim 1, wherein the ratio (by weight) of thefungicidal compound (b) to the azolopyrimidine of formula I (a) is from0.01:1 to 100:1.
 7. A method of controlling the growth ofphytopathogenic fungi at a locus which comprises applyingsynergistically effective amounts of the composition of claim 1 to thelocus.
 8. A method of controlling wheat leaf rust, wheat Septoria leafblotch and/or wheat powdery mildew at a locus which comprises applyingsynergistically effective amounts of the composition of claim 1 to thelocus.